CN114133602A - Preparation method of polyimide film without bubble defects - Google Patents
Preparation method of polyimide film without bubble defects Download PDFInfo
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- CN114133602A CN114133602A CN202111490513.1A CN202111490513A CN114133602A CN 114133602 A CN114133602 A CN 114133602A CN 202111490513 A CN202111490513 A CN 202111490513A CN 114133602 A CN114133602 A CN 114133602A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 33
- 230000007547 defect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000011347 resin Substances 0.000 claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 239000011265 semifinished product Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000005096 rolling process Methods 0.000 claims abstract description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 24
- 150000004985 diamines Chemical class 0.000 claims description 23
- 239000002798 polar solvent Substances 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 5
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 5
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000005187 foaming Methods 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract 2
- 239000004642 Polyimide Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A method for preparing a polyimide film free of bubble defects, comprising the steps of: preparing a bubble-free low viscosity compound solution or a bubble-free low viscosity mixture solution; introducing the prepared solution into a vacuum reactor for stirring to generate a high-viscosity resin solution; coating the carrier tape with the high-viscosity resin solution to form a wet film; passing the carrier tape coated with the high-viscosity resin solution through a thermal protective atmosphere furnace to obtain a semi-finished resin film product; stripping the semi-finished resin film from the carrier tape; placing the semi-finished product of the resin film separated from the carrier tape into a thermal protective atmosphere furnace for stretching to form a film; annealing the film and cooling to room temperature; and (5) rolling the film. The invention uses the non-foaming raw material with low viscosity, and the non-foaming raw material with low viscosity enters the vacuum reactor for polymerization, thereby preparing the high-viscosity resin solution with high viscosity and without re-defoaming, reducing the defoaming difficulty and simultaneously improving the quality of the prepared film.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a preparation method of a polyimide film without bubble flaws.
Background
The polyimide film has the characteristics of good photoelectric property, mechanical property, moisture barrier property and the like, is widely applied to the high and new technology industry fields of electrical insulating materials, Flexible Copper Clad Laminates (FCCL), flexible OLED displays, window films, new energy and the like, is mainly applied to flexible mobile phones, flat panels, televisions and other future intelligent display equipment, and is an indispensable key material of future flexible electronics.
The polyimide syrup is a resin solution, has a high viscosity, and is inevitably contaminated with air during the production of the polyimide syrup by a conventional polymerization method. At such high viscosity (viscosity of resin solution > 20 million CPS), the defoaming process of the polyimide slurry becomes extremely difficult, so that complete defoaming below the control value is not possible. If these bubbles are mixed into the final product, the quality defect of particle foreign matter is easily generated on the surface of the film product during production, which reduces the insulating property and strength of the film and affects the optical and mechanical properties of the product.
Disclosure of Invention
The invention provides a novel preparation method of a polyimide film without bubble defects, aiming at the defects that in the prior art, the optical and mechanical properties of a film product are affected due to the difficulty in bubble removal caused by high viscosity of polyimide slurry.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a preparation method of a bubble defect-free polyimide film, wherein the film has no bubble defect in a unit area after film formation, and the preparation method of the bubble defect-free polyimide film comprises the following steps:
a. preparing a bubble-free low-viscosity compound solution or a bubble-free low-viscosity mixture solution, wherein the viscosity of the bubble-free low-viscosity compound solution and the viscosity of the bubble-free low-viscosity mixture solution are both less than or equal to 10000 cps;
b. b, introducing the solution prepared in the step a into a vacuum reactor through a closed pipeline, mixing and stirring the solution under the vacuum degree of-0.1 MPa, wherein the stirring time is less than 360min, and carrying out polymerization reaction to generate a high-viscosity resin solution, wherein the viscosity of the high-viscosity resin solution is more than 200000 cps;
c. coating the high-viscosity resin solution on the surface of the carrier tape to form a wet film, wherein the thickness of the wet film is 0.01 mu m-20 mm;
d. passing the carrier tape coated with the high-viscosity resin solution through a thermal protection atmosphere furnace at the temperature of 80-150 ℃, and volatilizing 60-90% of solvent in the wet film to obtain a semi-finished resin film;
e. stripping the semi-finished resin film from the carrier tape;
f. placing the semi-finished product of the resin film separated from the carrier tape into a thermal protection atmosphere furnace at the temperature of 250-400 ℃ for further uniaxial or biaxial stretching to form a film;
g. annealing the film in an environment of 100-300 ℃, and cooling to room temperature after the annealing is finished;
h. and (5) rolling the film.
The invention uses low viscosity non-foaming raw material to make the non-foaming low viscosity raw material enter into vacuum reactor to polymerize, thus preparing high viscosity resin solution without re-foaming, and improving the quality of the prepared film while reducing the difficulty of defoaming.
The viscosity has important influence on the thorough degree of bubble removal, the smaller the viscosity is, the easier the bubble removal process is, the viscosity of the solution in the step a is less than or equal to 10000cps, the bubble removal of the solution is facilitated, and good conditions are provided for preparing the bubble-free high-viscosity resin solution subsequently.
Preferably, in the above method for preparing a bubble defect-free polyimide film, the bubble defect-free low viscosity compound solution in step a is obtained by the following steps:
a1. respectively dissolving dianhydride A and diamine A in a polar solvent A to obtain a solution A and a solution B;
a2. defoaming the product obtained in the step a1 under the vacuum degree of-0.1 MPa, wherein the defoaming time is less than 360 min;
the bubble-free low viscosity mixture solution in the step a is obtained by the following steps:
q1. dissolving dianhydride B and diamine B with low molecular weight in polar solvent B, mixing and stirring to generate prepolymer to obtain solution C;
and Q2, defoaming the product obtained in the step Q1 under the vacuum degree of-0.1 MPa, wherein the defoaming time is less than 360 min.
The invention removes the bubbles from the low-viscosity raw materials before reaction, and makes the non-bubble low-viscosity raw materials enter a vacuum reactor for polymerization, thereby preparing the high-viscosity resin solution with high viscosity and without removing the bubbles again, and improving the quality of the prepared film while reducing the difficulty of removing the bubbles.
Preferably, in the above method for preparing a polyimide film without bubble defects, in step B, when the solutions entering the vacuum reactor are solution a and solution B, the molar ratio of dianhydride a in solution a to diamine B in solution B is 0.9-1.2: 1; in the step B, when the solution entering the vacuum reactor is a solution C, the molar ratio of dianhydride B to diamine B in the solution C is 0.9-1.2: 1.
the reasonable proportion of dianhydride and diamine is one of the important factors influencing the molecular weight of the polymer. In actual production, the quality of dianhydride is affected by a small amount of water in a solvent and factors of raw materials, so that the ratio of dianhydride to diamine is not absolutely equal in actual production.
Preferably, in the above method for preparing a polyimide film without bubble defects, the molecular weight of the prepolymer in the solution C in the step Q1 is less than 5000.
The molecular weight of the polymer is one of the factors for determining the viscosity of the solution, and the proper molecular weight can ensure that the viscosity of the polymer solution is moderate, so that the defoaming and stirring processes are easy to perform.
Preferably, in the preparation method of the polyimide film without bubble defects, the polar solvent a and the polar solvent B are one or more of DMAC, DMF, DMSO, NMP, and tetrahydrofuran.
The aprotic polar solvent is an excellent solvent for preparing polyimide, not only provides a medium for polycondensation reaction, but also can better release reaction heat and can better disperse high polymer in the solvent.
Preferably, in the above method for preparing a polyimide film without bubble defects, the viscosity of each of the solution a, the solution B and the solution C is less than 5000 cps.
The viscosity of the solution is one of the key factors influencing the defoaming efficiency, and the dianhydride, the diamine or the low-molecular-weight prepolymer solution has the viscosity of less than 5000cps and can be better defoamed.
Preferably, in the method for preparing a polyimide film without bubble defects, the solution a, the solution B and the solution C are defoamed by a vacuum mechanical defoaming method.
For the low-viscosity solution, the vacuum mechanical defoaming is economical, does not introduce impurities and has high efficiency.
Detailed Description
The invention will now be described in further detail with reference to specific embodiments, but they are not intended to limit the invention:
example 1
A preparation method of a bubble defect-free polyimide film, wherein the film has no bubble defect in a unit area after film formation, and the preparation method of the bubble defect-free polyimide film comprises the following steps:
a. preparing a bubble-free low-viscosity compound solution or a bubble-free low-viscosity mixture solution, wherein the viscosity of the bubble-free low-viscosity compound solution and the viscosity of the bubble-free low-viscosity mixture solution are both less than or equal to 10000 cps;
b. b, introducing the solution prepared in the step a into a vacuum reactor through a closed pipeline, mixing and stirring the solution under the vacuum degree of-0.1 MPa for 355min, and carrying out polymerization reaction to generate a high-viscosity resin solution, wherein the viscosity of the high-viscosity resin solution is more than 200000 cps;
c. coating the high-viscosity resin solution on the surface of the carrier tape to form a wet film, wherein the thickness of the wet film is 20 mm;
d. passing the carrier tape coated with the high-viscosity resin solution through a thermal protection atmosphere furnace at the temperature of 50 ℃, and volatilizing 90% of solvent in the wet film to obtain a semi-finished resin film;
e. stripping the semi-finished resin film from the carrier tape;
f. placing the semi-finished product of the resin film separated from the carrier tape into a thermal protection atmosphere furnace at 400 ℃ for further uniaxial or biaxial stretching to form a film;
g. annealing the film in an environment of 300 ℃, and cooling to room temperature after the annealing is finished;
h. and (5) rolling the film.
Preferably, the bubble-free low viscosity compound solution in step a is obtained by:
a1. respectively dissolving dianhydride A and diamine A in a polar solvent A to obtain a solution A and a solution B;
a2. defoaming the product obtained in the step a1 under the vacuum degree of-0.1 MPa, wherein the defoaming time is 355 min;
the bubble-free low viscosity mixture solution in the step a is obtained by the following steps:
q1. dissolving dianhydride B and diamine B with low molecular weight in polar solvent B, mixing and stirring to generate prepolymer to obtain solution C;
and Q2, defoaming the product obtained in the step Q1 under the vacuum degree of-0.1 MPa, wherein the defoaming time is 355 min.
Preferably, in the step B, when the solution entering the vacuum reactor is the solution A and the solution B, the molar ratio of the dianhydride A in the solution A to the diamine B in the solution B is 1.2: 1; in the step B, when the solution entering the vacuum reactor is a solution C, the molar ratio of dianhydride B to diamine B in the solution C is 1.2: 1.
preferably, the molecular weight of the prepolymer in the solution C in the step Q1 is less than 5000.
Preferably, the polar solvent A and the polar solvent B are one or more of DMAC, DMF, DMSO, NMP and tetrahydrofuran.
Preferably, the viscosity of the solution A, the solution B and the solution C is less than 5000 cps.
Preferably, the defoaming method of the solution a, the solution B, and the solution C is vacuum mechanical defoaming.
Example 2
A preparation method of a bubble defect-free polyimide film, wherein the film has no bubble defect in a unit area after film formation, and the preparation method of the bubble defect-free polyimide film comprises the following steps:
a. preparing a bubble-free low-viscosity compound solution or a bubble-free low-viscosity mixture solution, wherein the viscosity of the bubble-free low-viscosity compound solution and the viscosity of the bubble-free low-viscosity mixture solution are both less than or equal to 10000 cps;
b. b, introducing the solution prepared in the step a into a vacuum reactor through a closed pipeline, mixing and stirring the solution under the vacuum degree of-0.1 MPa for 180min, and carrying out polymerization reaction to generate a high-viscosity resin solution, wherein the viscosity of the high-viscosity resin solution is more than 200000 cps;
c. coating the high-viscosity resin solution on the surface of the carrier tape to form a wet film, wherein the thickness of the wet film is 10 mm;
d. passing the carrier tape coated with the high-viscosity resin solution through a thermal protection atmosphere furnace at the temperature of 115 ℃ to volatilize 75% of solvent in the wet film, so as to obtain a semi-finished product of the resin film;
e. stripping the semi-finished resin film from the carrier tape;
f. placing the semi-finished product of the resin film separated from the carrier tape into a thermal protection atmosphere furnace at 325 ℃ for further uniaxial or biaxial stretching to form a film;
g. annealing the film in an environment of 200 ℃, and cooling to room temperature after annealing;
h. and (5) rolling the film.
Preferably, the bubble-free low viscosity compound solution in step a is obtained by:
a1. respectively dissolving dianhydride A and diamine A in a polar solvent A to obtain a solution A and a solution B;
a2. b, defoaming the product obtained in the step a1 under the vacuum degree of-0.1 MPa for 180 min;
the bubble-free low viscosity mixture solution in the step a is obtained by the following steps:
q1. dissolving dianhydride B and diamine B with low molecular weight in polar solvent B, mixing and stirring to generate prepolymer to obtain solution C;
and Q2, defoaming the product obtained in the step Q1 under the vacuum degree of-0.1 MPa, wherein the defoaming time is 180 min.
Preferably, in the step B, when the solution entering the vacuum reactor is the solution A and the solution B, the molar ratio of the dianhydride A in the solution A to the diamine B in the solution B is 1.05: 1; in the step B, when the solution entering the vacuum reactor is a solution C, the molar ratio of dianhydride B to diamine B in the solution C is 1.05: 1.
preferably, the molecular weight of the prepolymer in the solution C in the step Q1 is less than 5000.
Preferably, the polar solvent A and the polar solvent B are one or more of DMAC, DMF, DMSO, NMP and tetrahydrofuran.
Preferably, the viscosity of the solution A, the solution B and the solution C is less than 5000 cps.
Preferably, the defoaming method of the solution a, the solution B, and the solution C is vacuum mechanical defoaming.
Example 3
A preparation method of a bubble defect-free polyimide film, wherein the film has no bubble defect in a unit area after film formation, and the preparation method of the bubble defect-free polyimide film comprises the following steps:
a. preparing a bubble-free low-viscosity compound solution or a bubble-free low-viscosity mixture solution, wherein the viscosity of the bubble-free low-viscosity compound solution and the viscosity of the bubble-free low-viscosity mixture solution are both less than or equal to 10000 cps;
b. b, introducing the solution prepared in the step a into a vacuum reactor through a closed pipeline, mixing and stirring the solution under the vacuum degree of-0.1 MPa for 30min, and carrying out polymerization reaction to generate a high-viscosity resin solution, wherein the viscosity of the high-viscosity resin solution is more than 200000 cps;
c. coating the high-viscosity resin solution on the surface of the carrier tape to form a wet film, wherein the thickness of the wet film is 0.01 mu m;
d. passing the carrier tape coated with the high-viscosity resin solution through a thermal protection atmosphere furnace at the temperature of 80 ℃, and volatilizing 60% of solvent in the wet film to obtain a semi-finished resin film;
e. stripping the semi-finished resin film from the carrier tape;
f. placing the semi-finished product of the resin film separated from the carrier tape into a thermal protection atmosphere furnace at 250 ℃ for further uniaxial or biaxial stretching to form a film;
g. annealing the film in an environment of 100 ℃, and cooling to room temperature after annealing;
h. and (5) rolling the film.
Preferably, the bubble-free low viscosity compound solution in step a is obtained by:
a1. respectively dissolving dianhydride A and diamine A in a polar solvent A to obtain a solution A and a solution B;
a2. b, defoaming the product obtained in the step a1 under the vacuum degree of-0.1 MPa for 30 min;
the bubble-free low viscosity mixture solution in the step a is obtained by the following steps:
q1. dissolving dianhydride B and diamine B with low molecular weight in polar solvent B, mixing and stirring to generate prepolymer to obtain solution C;
and Q2, defoaming the product obtained in the step Q1 under the vacuum degree of-0.1 MPa for 30 min.
Preferably, in the step B, when the solution entering the vacuum reactor is solution a and solution B, the molar ratio of dianhydride a in the solution a to diamine B in the solution B is 0.9: 1; in the step B, when the solution entering the vacuum reactor is a solution C, the molar ratio of dianhydride B to diamine B in the solution C is 0.9: 1.
preferably, the molecular weight of the prepolymer in the solution C in the step Q1 is less than 5000.
Preferably, the polar solvent A and the polar solvent B are one or more of DMAC, DMF, DMSO, NMP and tetrahydrofuran.
Preferably, the viscosity of the solution A, the solution B and the solution C is less than 5000 cps.
Preferably, the defoaming method of the solution a, the solution B, and the solution C is vacuum mechanical defoaming.
In summary, the above-mentioned embodiments are only preferred embodiments of the present invention, and all equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the present invention.
Claims (7)
1. A preparation method of a polyimide film without bubble defects is characterized by comprising the following steps: the film has no bubble defect in unit area after being formed, and the preparation method of the polyimide film without the bubble defect comprises the following steps:
a. preparing a bubble-free low-viscosity compound solution or a bubble-free low-viscosity mixture solution, wherein the viscosity of the bubble-free low-viscosity compound solution and the viscosity of the bubble-free low-viscosity mixture solution are both less than or equal to 10000 cps;
b. b, introducing the solution prepared in the step a into a vacuum reactor through a closed pipeline, mixing and stirring the solution under the vacuum degree of-0.1 MPa, wherein the stirring time is less than 360min, and carrying out polymerization reaction to generate a high-viscosity resin solution, wherein the viscosity of the high-viscosity resin solution is more than 200000 cps;
c. coating the high-viscosity resin solution on the surface of the carrier tape to form a wet film, wherein the thickness of the wet film is 0.01 mu m-20 mm;
d. passing the carrier tape coated with the high-viscosity resin solution through a thermal protection atmosphere furnace at the temperature of 80-150 ℃, and volatilizing 60-90% of solvent in the wet film to obtain a semi-finished resin film;
e. stripping the semi-finished resin film from the carrier tape;
f. placing the semi-finished product of the resin film separated from the carrier tape into a thermal protection atmosphere furnace at the temperature of 250-400 ℃ for further uniaxial or biaxial stretching to form a film;
g. annealing the film in an environment of 100-300 ℃, and cooling to room temperature after the annealing is finished;
h. and (5) rolling the film.
2. The method for preparing a polyimide film free of bubble defects according to claim 1, wherein the method comprises the following steps: the bubble-free low viscosity compound solution in step a is obtained by:
a1. respectively dissolving dianhydride A and diamine A in a polar solvent A to obtain a solution A and a solution B;
a2. defoaming the product obtained in the step a1 under the vacuum degree of-0.1 MPa, wherein the defoaming time is less than 360 min;
the bubble-free low viscosity mixture solution in the step a is obtained by the following steps:
q1. dissolving dianhydride B and diamine B with low molecular weight in polar solvent B, mixing and stirring to generate prepolymer to obtain solution C;
and Q2, defoaming the product obtained in the step Q1 under the vacuum degree of-0.1 MPa, wherein the defoaming time is less than 360 min.
3. The method for preparing a polyimide film free of bubble defects according to claim 2, wherein: in the step B, when the solution entering the vacuum reactor is solution A and solution B, the molar ratio of dianhydride A in the solution A to diamine B in the solution B is 0.9-1.2: 1; in the step B, when the solution entering the vacuum reactor is a solution C, the molar ratio of dianhydride B to diamine B in the solution C is 0.9-1.2: 1.
4. the method for preparing a polyimide film without bubble defects according to claim 3, wherein: the molecular weight of the prepolymer in the solution C in the step Q1 is lower than 5000.
5. The method for preparing a polyimide film without bubble defects according to claim 3, wherein: the polar solvent A and the polar solvent B are one or more of DMAC, DMF, DMSO, NMP and tetrahydrofuran.
6. The method for preparing a polyimide film without bubble defects according to claim 3, wherein: the viscosity of the solution A, the solution B and the solution C is less than 5000 cps.
7. The method for preparing a polyimide film without bubble defects according to claim 3, wherein: the defoaming mode of the solution A, the solution B and the solution C is vacuum mechanical defoaming.
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| CN202111490513.1A CN114133602B (en) | 2021-12-08 | 2021-12-08 | Preparation method of bubble-defect-free polyimide film |
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| CN202111490513.1A CN114133602B (en) | 2021-12-08 | 2021-12-08 | Preparation method of bubble-defect-free polyimide film |
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| CN114133602B CN114133602B (en) | 2023-11-14 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020074686A1 (en) * | 2000-09-11 | 2002-06-20 | Katsunori Yabuta | Process for preparing polyimide film |
| CN108699242A (en) * | 2016-09-23 | 2018-10-23 | 株式会社Lg化学 | polyimide precursor solution and its manufacturing method |
| CN110117362A (en) * | 2018-02-05 | 2019-08-13 | 中天电子材料有限公司 | Kapton and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020074686A1 (en) * | 2000-09-11 | 2002-06-20 | Katsunori Yabuta | Process for preparing polyimide film |
| CN108699242A (en) * | 2016-09-23 | 2018-10-23 | 株式会社Lg化学 | polyimide precursor solution and its manufacturing method |
| CN110117362A (en) * | 2018-02-05 | 2019-08-13 | 中天电子材料有限公司 | Kapton and preparation method thereof |
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